Electronic structure of cation-codoped TiO2 for visible-light photocatalyst applications from hybrid density functional theory calculations

Abstract

The electronic structures of Mg/Ca- and/or Mo/W- (mono- and co-) doped anatase TiO2 have been investigated via generalized Kohn–Sham theory with the Heyd–Scuseria–Ernzerhof hybrid functional for exchange-correlation {J. Heyd et al., [J. Chem. Phys. 118, 8207 (2003)], J. Heyd et al., [J. Chem. Phys. 124, 219906 (2006)], and J. Paier et al., [J. Chem. Phys. 125, 249901 (2006)]}, in the context of density functional theory. Gap narrowing is small for monodoping, which also creates impuritiy bands in the “forbidden gap,” either as acceptor or donor states, limiting possible utility as visible-light photocatalysts. However, codoping of Mg/Ca and Mo/W not only induces appreciable gap narrowing, but also serves to passivate the impurity bands, which can harvest visible-light to a greater extent. Considering ionic radii, Mg and Mo should constitute the best cation-pair.